Triazole dyestuffs



Patented July 27, 1954 TRIAZOLE DYESTUFFS Ernst Keller and ReinhardZweidler, Basel, Switzerland, assignors to J.

Switzerland R. Geigy A. G., Basel,

No Drawing. Application January 21, 1953, Serial No. 332,500

Claims priority, application Switzerland January 21, 1952 6 Claims.

The present invention concerns the production of new dyestuifs, thedirect dyeings of which on cellulose fibres fluoresce to a, greater orlesser degree in ultraviolet light according to the composition thereof.It is due to this property that they produce a luminous effect which hasnever before been attained.

It has been found that by coupling tetrazotised 1.4 di (4'-aminostyryl)-benzene compounds with aromatic amino compounds coupling in theo-position to an amino group, dis-o-aminoazo dyestuffs can be obtainedwhich can be oxidised by methods known per se to form the corresponding1.4-di-[4'-(arylo-1.2.3-triazolyl 2) styryl] benzene compounds of thegeneral formula:

As aromatic amino compound coupling in the o-position to an amino group,preferably those of the benzene and naphthalene series are employed inthe process according to the present invention, e. g.1.3-diaminobenzene, 1.3-diamino- -methylor -4-chlorobenzene,1.3-diaminobenzenei-sulphonic acid, 5-chloro-l-aminonaphthalene,l-aminonaphthalenelor -5-sulphonic acid, 2-aminonaphtha1ene,2-amino-6-methoxynaphthalene, 2-amino-naphthalene-5-, -6- or-7-monosulphonic acid, 2 aminonaphthalene- 3.6- or -5.7-disulphonicacids, etc. It is also possible, however, to use heteroeyclic aromaticamino compounds coupling in the o-position to an amino group, e. g.2-phenyl-5-amino-1.2.3- benztriazole and similar compounds.

In this formula A represents an aromatic radi= cal bound by neighbouringcarbon atoms to the nitrogen atoms of the 1.2.3-triazole ring. All thearomatic radicals of these triazole compounds can be further substitutedas desired, e. g. by halogen, alkyl, alkoxy, amino, acylamino, carboxyland sulphonic acid groups.

Insofar as they contain no further chromophores, such as e. g. arylazogroups, these new lA-di-(4'-arylotriazolyl styryl) benzene compounds areyellow dyestuils, the dyeings of which in ultraviolet light fiuorescemore or less intensively according to the composition of the light andthe substrate. and, therefore, in daylight they produce shades of pureluminosity which have :3. hitherto never been attained. This is truepar-' ticularly of the direct dyeings on cellulose.

The most suitable compound for the-production of textile dyestuffsaccording to the process of the present invention isthe1.4-di-(4'-amino- 2-sulphonic acid styryl) benzene compound. Thiscompound is obtained according to the process of the patentspecification Ser. No. 214,014, new U. S. Patent No. 2,657,228 grantedOctober 27, 1953, by condensing terephthalaldehyde with5-nitro-2-methylbenzene-l-sulphonic acid aryl esters, saponifying thesulphonic acid aryl ester and reducing the nitro group to the aminogroup. The aqueous solution of its alkali salts can easily betetrazotised according to the indirect method a with sodium nitrite andmineral acid and coupled in a neutral to weakly acid medium witharomatic amino compounds coupling in the o-position to the amino groupto form the dis-o-aminoazo dyestufi. I

The dis-o-aminoazo dyestuifs are oxidised to form the correspondingarylo-l.2.3-triazolyl compounds by methods known per se, for example inaqueous solution or suspension or in organic solvents which are stableto oxidation. As oxidation agents can be used for example thecupritetrammine salts and the salts of hypochlorous acid. It is oftenadvantageous to reduce the oxidation products afterwards, for example toreact them with sodium hydrosulphite in order to convert any1.2.3-triazole oxide into 1.2.3-triazole compounds. Also, any functionalgroups present in the end products can be altered afterwards, e. g.amino groups by acylation, insofar as this is desired and it isadvantageous to do so.

As already mentioned, it is advantageous for textile purposes to use1.4-di-(4'-aminostyryl)- benzene-2.2-disulphonic acid, the tetrazocompound of which can be coupled advantageously with such azo componentsas contain acid Watersolubilising groups, such as carboxyl or sulphonicacid groups. Particularly favourable azo components for the productionof water soluble dyestuffs having an afiinity to cellulose fibresaccording to the present invention are the aminonaphthalene sulphonicacids coupling in the o-position to the amino group, and of these,particularly Z-aminonaphthalene 5.7 disulphonic acid, because itproduces the most pure dyestuffs according to this invention.

The new 1.4-di- [4'-(arylo-1.2.3-triazcly1-2) styryll-benzene compoundsare yellow powders and, insofar as they contain acid water-solubilisinggroups, in the form of their alkali salts they dissolve in water with ayellow colour. They have a marked afiinity, varying according to the2-aminonaphthalene-5-sulphonic acid, the socomposition, to cellulosefibres. dium salt of 1.4-di-[4-(naphtho-1".2":4.5-

The following examples illustrate the inven- 1.2.3-triazolyl-2) styryll-benzene 2.2.5".5"- tion without limiting it in any way. Where nottetrasulphonic acid is obtained as a yellow-brownotherwise stated, partsare given as parts by ish powder.v The cellulose dyeing of thiscomweight and the temperatures are in degrees centipound is a moregreenish yellow shade and has grade. The relationship of parts by volumeto the same interesting properties as the product parts by Weight is asthat of kilogrammes t0 described above.

litres. Ermmpze 2 Example 1 The tetrazo suspension prepared according toExample 1 from 47.2 parts of 1.4-di-(4'-amino- 2.2disulphonic acid aredissolved with sodium y n n -2'.2'-disu1phonic acid is added athydroxide in 1400 parts of hot water. The solu- Iii-12 to a solution of60.6 D ts 0f tion should have a neutral reaction. An aqueous p e -5- -dS D C acid, Parts Of solution of 13.8 parts of sodium nitrite is then im y r i an 50 parts of crystallised added and the whole is indirectlydiazotised at sodium eeetatein 0 p r f W On p 10-12 with 50 parts ofconcentrated hyd1'o n f e pl n the dyestuff is completely chloric acid.The Whole is stirred for half an p pi by the i n f od um chl ri e hourand then the suspension of the tetrazo com- 20 d filtered The p dy tufiS then c mpound is added at 10-12 to a solution of 44.6 part pletelydissolved in hot water with the addition of of2-aminonaphthalene-6-sulphonic acid which 0 parts f 5% mm ni an i oxdised at has been dissolved in 500 parts of water with 8.2 9 to form e tly o po d W t a parts of sodium hydroxide and 50 parts of crysiX e Of120 p s o crystallised pp Su tallised sodium acetate. On completion ofthe p e in 80 P s Of W t a d 0 Pa t Of coupling, the dyestuff iscompletely precipitated ammonia. The copper is removed from the prodbythe addition of sodium chloride and filtered uct as described inExamp 1. With Sodium 11-.- 011. The damp dyestufi' is then completelydisp e. he p od is pu d whereupon the solved in water with the additionof 40 parts of sodium salt of 1.4-di-[4-(naphtho-l".2"24.5- 25% ammoniaandasolution of 120 parts of crys- 30 1.2.3 triazolyl 2) styryl]benzenetallised copper sulphate in 430 parts of water to2'.2'.5".5.7.7"-hexasulphonic acid of the 47.2 parts of1.4-di-(4-aminostyryl)--benzenewhich 240 parts of 25% ammonia has beenadded formula:

s oin 803E HOaS- N\ /N SOaH S0311 N is added at 92-97". The whole iskept for several is obtained as a yellow-brown powder. The comhours at9297 until the azo dyestuff has compound is easily soluble in water, thesolutions are pletely disappeared. It is then allowed to cool a pureyellor colour. When dyed on to cellulose and the ditriazolyl compound issalted out by the fibres, greenish-yellow dyeings are obtained ofaddition of sodium chloride. The raw product in extraordinary purity andluminosity in daylight. the presence of an excess of sodium sulphide isThe dyeings on cellulose have good fastness dissolved in hot water, thecopper sulphide which properties. In ultraviolet light they have aradiforms is filtered off, the excess alkali sulphide ant.greenish-yellow colour. The compound can compound is decomposed withhydrochloric acid, also be dyed on to wool and silk from an acid bath,and the product is further purified by recrystallion which it producesvery pure greenish-yellow sation from water with the addition of alittle dyeings.

sodium hydrosulphite and animal charcoal. The If in the above example,the 2-aminonaphtha-. sodium salt of 1.4-di- [4-(naphtho-1".2":4.5-lene-5.7-disulphonic acid is replaced by 60.6 parts 1.2.3-triazolyl-2)styryl] benzene 2'.2'.6".6"- of 2-aminonaphthalene-6.8-disulphonic acid,the tetrasulphonic acid of the formula: sodium salt of1.4-di-[4'-naphtho-1".2":45-

is obtained as a brownish yellow substance. 1.2.3 triazolyl 2) styryllbenzene-v Dyed on to cellulose fibres, in daylight this2'.2.6".6".8.8"-hexasulphonic acid is obtained compound produce ahitherto unobtained lumias a yellow-brown powder. Dyed on to cellulose,nous yellow shade. In ultraviolet light fibres this compound produces areddish yellow shade dyed therewith luminesce a brilliant yellow. Theand the dyeing has interesting properties similar fastness properties ofthe dyeings on cellulose are to t product described above good. Also,wool and silk can be dyed in a weakly acid bath; the dyeings obtainedhave pure shades and fluoresce very strongly in ultraviolet light.

If in the above example, the 2-aminonaphtha- 47.2 parts ofl.4-dl-(4'-ami 0S y yl z elene-G-sulphonic acid is replaced by 44.6parts of 75 2'.2-disulphonic acid are indirectly diazotised Example 3described in Example 1 and the tetrazocom'pound dissolved in hot waterwith "the addition of 40 is coupled with a solution of 21.7 parts of1.3- parts of 24% ammonia and oxidised at'92-97" diaminobenzene andparts of concentrated hywith a mixture of'120 parts of crystallisedcopper drochloric acid in 400 parts of water. A solution sulphate in 480parts of water and 240 parts of of 77 parts of crystallised sodiumacetate is slowly 5 ammonia to form the ditriazoly'l' compound. addeddropwise at 10-12. After the tetrazo com- The copper'is removed withsodium sulphide and pound has completely disappeared, the dyestufi theproduct is purified as described in Example 1. is salted out andfiltered off. The filter cake is The sodium salt of1.4-di-[4-(5"-aminobenzodissolved in hot water with the addition of1.2:4.5 1.2.3 triazolyl 2) styryl] benparts of 25% ammonia and isoxidised at 9297 10 zone-2.2'.4".4"-tetrasulphonic acid of the forwith amixture of 120 parts of crystallised copper mula:

' .'NH N A0311 AOaH N 80311 sulphate in 480 parts of water and 240 partsof is obtained as a brownish yellow powder. The 25% ammonia. The copperis removed from the aqueous solutions of the alkali salts of thiscomditriazolyl compound as described in Example 1 20 pound are pureyellow. A yellow dyeing with a and the dyestufi is purified. The sodiumsalt of very pure nuance is obtained on cellulose fibres.

1.4 di [4 (5" aminobenzo l.2":4.5- The solutions and dyeings of thisproduct show 1.2.3 triazolyl 2) styryl] benzene 2.2'-di a strongbrilliant yellow luminescence in ultrasulphonic acid of the formula:violet light.

N N V HzN NH:

7 \N/ 403E A0311 \N is obtained as a brown sh-yellow powder- The If thecompound described in the above examaqueous solutions of the alkalisalts are yellow ple is acetylated,1.4-di-[4'-(5"-acetaminobenzocoloured. When dyed on to cellulose fibres,an 1".2":4.5 1.2.3 triazolyl 2) styryl] benintense yellow dyeing isobtained which fiuoresces zene-2.2'.4".4"-tetrasulphonic acid isobtained.

strong yellow in ultraviolet light. The dyeings of this compound oncellulose fibres 1.4 di [4 (5" ac t m o beIlZO- 35 While havingotherwise similar properties, are a 1".2":4.5 1.2.3 triazolyl 2) styryl]benmore greenish yellow than those of the unacetzene-2'.2'-disulphonicacid is obtained by acetylated d t,

ylating the compound described above in the example. This compound,which otherwise has Example 5 similar properties, producesamore greenishshade 47.2 parts of 1.4-di-(4-aminostyryl)-benzeneon cellulose fibres.2'.2'-disulphonic acid are indirectly diazotised as If in the aboveexample, the m-phenylene didescribed in Example 1. A solution of 37.5parts amine is replaced by 27.4 parts of 1-amino-4- of2.3-aminonaphthoic acid, 82 parts of sodium methyl-S-methoxybenzene, thesodium salt of hydroxide and parts of crystallised sodium ace- 1.4 di[4' (4" methyl 5" methoxy-benzo- 45 tate in 500 parts of water is addedto the suspen- 1".2":4.5-1.2.3-triazolyl 2) styryl] benzenesion of thetetrazo compound at a temperature of 2'.2-disulphonic acid of theformula: 10-12". On completion of the coupling, the dyeis obtained as abrownish yellow powder. When stuff is precipitated by the addition ofsodium dyed on to cellulose fibres this compound also chloride andfiltered oiT. The damp dyestuff is produces an intensive yellow dyeingwhich has dissolved by the addition of 40 parts of 25% ampropertiessimilar to those of the product demonia in hot water and oxidised at atemperature scribed above. of 92-97 with a mixture of parts of crystal-Example 4 lised copper sulphate in 480 parts of water and A suspensionof a tetrazo compound produced 60 240 Parts Of ammonia form theditliazolyl according to Example 1 from 47.2 parts of 1.4-dicompounde pr 15 removed y repeated (4'-aminostyryl)-benzene-2'.2-disulphonic acidboiling 0111? With hydrochloricacid, the dyeis added at 10-12 to aneutral solution of 37.6 stufi is pasted in xc s 2% sodium carbonateparts of 1 3 diaminobenzene 4 sulphonicacid, solution and the sodiumsalt of 1.4-di-[4-(naph 8.2 parts of sodium hydroxideand 50 parts of t"-2": 1.2- olyl 2) styry1lcrystallised sodium acetate in 500'parts ofwater. benZenB-3"-3"-d10arb0Xy-2 -d1su1ph0m0 acld On completion of thecoupling, the dyestufi is of the formula:

OaH OaH N- coon H000 salted out and filtered off. The damp dyestuff isis obtained as a'yellow-brown powder.

Dyed on to cellulose fibres, this compound produces a yellow shade whichis luminous in daylight. In ultraviolet light, fibres dyed therewithshine a radiant yellow. The compound can also be dyed from an acid bathon to wool and silk and then produces very pure, greenish yellowdyeings.

N A CH=CHOCH=CH Example 6 10 parts of cotton are treated for 60 minutesat 90 in a bath (liquor ratio 1:40) containing 2% (calculated on theweight of the fibres) of the sodium salt of 1.4-di- [4'-naphtho-1.2:4.5-1.2.3 triazolyl 2) styryl] benzene- 2.2.5".5".'7.7"-hexasulphonic acidobtained according to Example 2, 50% of Glaubers salt and 1% of soda(calculated on the weight of the fibres). After rinsing and drying, indaylight the material has a brilliant greenish yellow colour of a puritywhich has hitherto never been attained.

What we claim is:

1. A triazole dyestuff having the general formula:

SOaH 0311 wherein A represents an aromatic radical selected from thegroup consisting of the benzene and naphthalene series bound byneighbouring carbon atoms to the nitrogen atoms of the 1.2.3-triazo1ering.

2. A triazole dyestuff having the formula:

5103B SOZH HO3S N /N 80311 N/ scan $0311 N/ 3. A triazole dyestuffhaving the formula:

Ho3s -s0311 N /N N/ $103K 0315! N 4. A triazole dyestuff having theformula:

HOaS N /N 80311 N/ 403E so3H N 5. A triazole dyestufl having theformula:

N OJH SOaH N noon JOOH 6. A triazole dyestufi having the formula: N NHzCOC-HN- -NHCOCH:

HOaS- sOaH N 01H s'our N/ References Cited in the file of this patentUNITED STATES PATENTS Number Name Date 2,467,262 Knight Apr. 12, 1949FOREIGN PATENTS Number Country Date 590,426 Great Britain July 17, 1947603,267 Great Britain June 11, 1948 OTHER REFERENCES Charrier, Chem.Abstracts, vol. 24, page 366

1. A TRIAZOLE DYESTUFF HAVING THE GENERAL FORMULA: 